Esters of sulfo high fatty acids with oxyalkylated phenol aldehyde resins



Patented Jan. 8, 1952 ES-TERS OF SULFO HIGH FATTY ACIDS WITH OXYALKYLATED PHENOL ALDE- HYDE RESINS Melvin De Groote, St. Louis, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 10, 1948, Serial No. 64,451

12 Claims. 1

The present invention is concerned with certain new chemical products, compounds or compositions, having useful application in various arts. This invention is a continuation-in-part of our co-pending application, Serial No. 734,204, filed March 12, 1947, and now abandoned. It includes methods or procedures for manufacturing said new products, compounds or compositions, as well as the products, compounds or compositions themselves.

Said new compositions are the esters of a sulfo higher fatty acid having at least 8 carbon atoms and not more than 22 carbon atoms in the fatty acid acyl group and in which the hydrogen atom of the sulfo radical has been replaced by a cation, and the ester linkage involved is by virtue of the higher fatty acid carboxylic radical and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of, a plurality of divalent radicals having the formula (12.10), in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase ofthe emulsion. This specific application is described and claimed in our co-pending application, Serial No. 64,450, filed December 10, 1948, now Patent No. 2,541,994, issued February 20, 1951. See also our co-pending application, Serial. No. 64,469, filed December 10, 1948.

The new products are useful as wetting, detergent and levelling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents andspreaders in the application of asphalt in road building and the like; as av flotation reagent in the flotation separation of various aqueous suspensions con: taining negatively charged particles such as s'ewage, coal washing Waste water, and varioustrade wastes and the like; asgermicides, insecticides, emulsifying agents, as for example, for cosmetics, spray oils, water-repellent textile finishes; as lu: bricants, etc. p

The oxyalkylated resins, used to provide the alcoholic radical of the new esters, are described in our Patents 2,499,370, granted March 7, 1950, and 2,541,991, granted February 20, 1951, and reference is made to those patents for a description of the phenol-aldehyde resins used and their oxyalkylation to produce the alcoholic products. For specific examples of the resins, refer ence is made to Examples 1a through 1031101 Patent 2,499,370. For examples of the oxyal kylated products, reference is 'made to Examples 1b through 18b of Patent 2,499,370 and to the tables which appear in columns 51 through 56 thereof, and also is made to the tables which appear in columns 31 through 46 of Patent 2,541,991. V g

Having prepared or purchased suitable oxyal kylated derivatives to be used as alcoholic re actants, one must either purchase or prepare suitable sulfo derivatives of the kind previously described. Such sulfo derivatives may be ex-'- emplified by the following:

Ewample 1c Sulfo oleic acid ethyl ester ammonium salt is prepared as per directions in-U. S. Patent No, 1,822,977 to Miinz.

Example 20 Example 30 The sulfo ricinoleic acid isopropyl alcohol ester triethanolamine salt is prepared as per directions in aforementioned U. S. Patent No. 2,032,314 to Bertsch.

Example 40 Sulfo oleic acid normal propyl est-er triethanolamine salt is prepared according to directions in aforementioned Bertsch Patent No. 2,032,314.

Example 50 Sulfo oleic acid methyl ester monoethanolamine salt is prepared as per directions in aforementioned U. S. Patent No. 1,822,978 to Miinz.

Example 60 Butyl sulfoxylylstearate sodium salt is pre pared according to the directions in U. S. Patent No. 2,302,070 dated November 17, 1942,, to Stirton, Peterson, and Groggins.

Example To Methyl sulfoxylylstearate sodium salt is prepared according to the directions in aforementioned U. S. Patent No. 2,302,070 to Stirton et al.

Example 80 Butyl sulfocymylstearate ammonium salt is prepared. from normal butyl oleate and paracymene according to the. directions in aforementioned Patent No. 2,302,070.

Having available the polyhydroxylated reac tant, i.e., the reactant obtained by oxyalkylation of the phenol resins, one need. only cause cross-esterification or. transesterification to take place by the. elimination of the. low molal al cohol which occupies the carboxylic hydrogen position in, the. sulfo fatty reactant. Such reaction is. essentially an alcoholysis reaction in which. the low molal alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, normal propyl alcohol, butyl alcohol, or the like is eliminated. As is well known, such reactions are catalyzed by the presence of an alkaline substance; approximate /'z% to 1% of an alkaline substance such as sodium acetate, sodium oleate, sodium carbonate, sodium methylate, caustic potash, or the like, may be added. Similarly, such reactions are catalyzed by a variety of other substances such as calcium or lead naphthenates, etc. Our preference is. to use approximately /2% of sodium methylate as a catalyst. The hydroxyl value of-thepolyhyd-ric alcohol can be calculated, based on the. value of the reactants, or can be determined by the Verley Bolsing method or any other suitable method... Having calculated the hydroxyl value, one can also calculate the appropriate amount of sulfo fatty reactant required for the complete esterification or complete conversion into the corresponding sulfo fatty acid ester with the elimination of the low molal alcohol. We have found that desirable products are obtained by conversion of as little as 20% to 25% into the sulfo fatty acid esters. In other words, on conducting our reaction we may vary from five stoichiometric equivalents of the polyhydric reactant in comparison to the sulfo fatty acid ester, or we may employ completely equivalent amounts, that is, for each five stoichiometric equivalents of the polyhydric acylating reactant, i. e., the sulfo acid ester. Comparison of the reaction can be determined in the customary manner, for instance, by measuring the amount of lowmolal alcohol evolved or by a saponification number on the finished product, or by any other suitable procedure.

Example 1d 1111 pounds of an oxyalkylated thermoplastic phenolaldehyde resin as exemplified by Exampie 1221) of Patent 2,541,991, were treated to remove xylene and reacted with pounds of sulfo oleic acid methyl ester ammonium salt to effect approximately a 20% acylation. The reaction. was conducted at approximately to C. for 2 to 4 hours, using of sodium methylate as a catalyst. Methyl alcohol was evolved and the completion of the reaction was indicated by the fact that there was no further evolution of methyl alcohol. The entire mass, of course, was agitated continuously during the acylation reaction. 7

Example 2d The same procedure was followed as in Exam.- ple 1d, preceding, except that sufiicient. acylation reactant was added to convert 50% of available hydroxyl into the ester form (50%. acylation). As a specific example, the following raties were employed: 1328.7 grams of xylenecontaining oxyalkylated resin 1231) of Patent 2,541,991 were reacted with 213 grams of sulfo oleic acid methyl ester ammonium salt as in Example 1d.

Example 311 The same procedure was followed as in Examples 1d and 2d, preceding, except that the amount of sulfo oleic acid. methyl ester ammonium salt employed was suflicient to esterify all available hydroxyl groups (complete, acylation). As a specific example, the following ratios were employed: 854 grams of xylene-containing oxyalkylated resin 11Gb of Patent 2,541,991 were reacted with 426 grams of sulfo oleic acid methyl ester ammonium salt as in Example 1d.

Example 411 The same procedure was followed as in Exampl 1d preceding, except that sulfo ricinoleic acid ethyl ester ammonium salt was used instead of sulfo oleic acid methyl ester ammonium salt in Examples id to 3d, precedingj As a specific example, the following ratios were employed: 511 grams of xylene-containing oxyalkylated resin 1251) of Patent 2,541,991 were reacted with 213 grams of sulfo ricinoleic acid ethyl ester ammonium salt as in Example 1d.

Example 5d The same procedure was followed as in Examples id to 3d, preceding, except that sulfo linoleic acid isopropyl ester ammonium. salt was used in place of, sulfo oleic acid methy .v ester am,- monium salt. As a specific example, the follow-. ing ratios were employed: 973 grams of xylene-l. containing resin 12Gb of Patent 2,541,991 was reacted with 435 grams of sulfo linoleic acid iso-. propyl ester ammonium salt as in Example 1d.

Example 6dv The same procedure was followed as in Examples lcl to 3d, preceding, except that butyl sulfoxylylstearate ammonium salt was employed instead of sulfo oleic acid methyl ester ammo nium salt. As a specific example, the following ratios were employed: 751 grams of xylene-con taining oxyalkylated resin 1415 of Patent 2,541,991 were reacted with 308 grams of butyl sulfoxylylstearate ammonium salt as in Example 1d.

Example 7d The same procedure was followed as in Example 1d preceding, except that butyl sulfocymylstearate ammonium salt was used instead involved is by virtue of the higher fatty 'acid car-- of sulfo oleic acid methyl ester ammonium salt; As a specific example, the following ratios were,

employed: 903 grams of xylene-containing oxyal kylated resin 13% of Patent 2,541,991 were re-' acted with 230 grams of butyl sulfocymylstearate ammonium salt asin Example 111.

As .previously pointed out the oxyalkylated resins, such as Example 122!) of Patent 2,541,99l employed in Example 1d, preceding, are obtained in a form which includes xylene as a solventf i The xylene was removed in the conventional manner as referred to "elsewhere by distillation,

particularly vacuum distillation. However, if desired, the, xylene need not be removed and the experiments previously noted, for instance, Ex amples 1d to 7d, inclusive, can be repeated leaving the xylene present. Under such circumstances the alcohol liberated, for instance, methyl alcohol, is not evolved but stays dissolved in the xylene In such instance'the reaction chamber should be equipped with a condenser and the conventional equipment. The completeness of the reaction can be determined by the fact that the xylene can be washed to remove the alcohol and, the decrease in volume noted. We have em ployed both procedures without noting any par-. ticular difference in the composition of the ultimate product. However, if this latter procedure is employed we must prefer to use the methyl or ethyl ester rather than the butyl ester, or even a higher alcohol ester, such as the-amyl ester; g

. gThe oxyalkylated resins, as far as appearance goes, have a resinto wax-like and fat-like character and color aries from light amberto deep amber, or reddish color The sulfo reactants generally vary in appearance from a honey yellow toa deep red or dark amber color. products of reaction, that is, the new compositions as described, will vary in appearance ona solvent-free basis, from an amber to a deep amber or reddish amber in color, and viscosity may vary somewhat from that of an oil to that of a heavybodied castor oil, or thereabouts.

It is to be noted that the salt form of the sulfo fatty acid ester is not limited to the sodium, ani--'v monium or potassium form, or even to the form employing low. molal amines, 1 for butylamine, amylamine, acetylamine, etc. Our preference, however, is to use either the ammonium, sodium, or potassinm salt or a non instance, ethanolamine, diethanolamine, triethanolamirie hydroxylated amine and particularly a tertiary amine of definite basicity, such as dimethyloctyl amine, dimethyloctadecylamine, dimethyldecyl It is to be r amine, dimethyldodecylamine, etc. noted that when a high molal amine is used, for

instance, one having present at least one radical obtained from higher fatty acids having as few. as 11 carbon atoms, as in the case of undecylic acid, and as many as 22 carbon atoms, as in the" case of fatty acids derived from jojoba bean oil: We claim:

boxylic radical and the alcoholic radical is that of certain hydrophile polyhydric synthetic prod-'- ucts; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon, atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide; glycide and methylglycide, and (B) anoxyalkylation-susceptible, fusible, organic solvent-soluble,

water-insoluble phenol-aldehyde resin; 7 said resin being derived by reaction between a difunc-- tional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula at the phenolic hydroxyls of a plurality of di-.

valent radicals having the formula (R1O)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals,

and hydroxybutylene radicals, and n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus. 1 V 1 2. An ester of a sulfc high fatty acid having at least 8 carbon atoms and not more than 22 carbon atoms in the fatty acid acyl group and in which the hydrogen atom of the sulfo radical has been replaced by a cation, and the ester linkage involved is by virtue of the higher fatty acid car boxylic radical and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; such hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylation-susceptible, fusible, [or-.- ganic solvent-soluble, water-insoluble phenol aldehyde resin; said resin being derived. by reac-- tion between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the sub stantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radiaasnsvs eels having theformula (CQHrOM; wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be intro? duced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water;

3. An ester of a sulfo high fatty acid having at L least 8 carbon atoms and not more than 22 carbon atoms in the fatty acid acyl group and in which the hydrogenatom of the sulfo radical has been replaced by a cation, and the ester linkage involvedis by virtue of the higher fatty acid earboxylic radical and the alcoholic radical isthat of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylation-s'usceptible, fusible, organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average "molecular weight corresponding to at least 3 and not over '7 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least rand not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (CsiHsOM; wherein 1i is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight'of xylene are sumcient to produce an emulsion when said Xylene solution is shaken vigorously with oneto three volumes of water.

v 4. An ester of a sulfo high fatty acid having a least 8 carbon atoms and not more than 22 car,- bon atoms in the fatty acid acyl group and in which the hydrogen atom of the sulfo radical has been replaced by a cation, and the ester linkage involved is by virtue of the higher'iatty acid car'boxylicradical and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide; and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, water, insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 7 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional'monohydric' phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greatenthan two; said phenol being of the formula characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophlle properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of Water.

5. The product of claim 3 wherein R is substituted in the para position.

6. The product of claim 3 wherein R is a butyl radical substituted in the para position.

'7. The product of claim 3 wherein R is an amyl radical substituted in the para position.

8. The product of claim 3 wherein R is a nonyl radical substituted in the para position.

9. The product of claim 4 wherein R is sub stituted in the para position.

10. The product of claim 4 wherein R is a butyl radical substituted in the para position.

11. The product of claim 4 wherein R is an amyl radical substituted in the para position.

'12. The product of claim 4 wherein R. is a nonyl radical substituted in the para position.

No references cited. 

1. AN ESTER OF A SULFO HIGH FATTY ACID HAVING AT LEAST 8 CARBON ATOMS AND NOT MORE THAN 22 CARBON ATOMS IN THE FATTY ACID ACYL GROUP AND IN WHICH THE HYDROGEN ATOM OF THE SULFO RADICAL HAS BEEN REPLACED BY A CATION, AND THE ESTER LINKAGE INVOLVED IS BY VIRTUE OF THE HIGHER FATTY ACID CARBOXYLIC RADICAL AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE SYNTHETIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYLKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCITIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA 